Alkanolamine semiconductor process residue removal composition and process

ABSTRACT

A two carbon atom linkage alkanolamine compound composition comprises the two carbon atom linkage alkanolamine compound, gallic acid or catechol, and optionally, an aqueous hydroxylamine solution. The balance of the composition is made up of water, preferably high purity deionized water, or another suitable polar solvent. A process for removing photoresist or other residue from a substrate, such as an integrated circuit semiconductor wafer including titanium metallurgy, comprises contacting the substrate with the composition for a time and at a temperature sufficient to remove the photoresist or other residue from the substrate. Use of the two carbon atom linkage alkanolamine compound in the composition and process provides superior residue removal without attacking titanium or other metallurgy, oxide or nitride layers on the substrate.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation-in-part of application Ser. No. 08/628,060, filed Apr. 17, 1996, which is in turn a continuation-in-part of application Ser. No. 08/078,657, filed Jun. 21, 1993, which is in turn a continuation-in-part of application Ser. No. 07/911,102, filed Jul. 9, 1992, now U.S. Pat. No. 5,334,332, which was a continuation-in-part of application Ser. No. 07/610,044, filed Nov. 5, 1990, now U.S. Pat. No. 5,279,771. The disclosures of those applications are hereby incorporated by reference in this application.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] The present invention relates generally to a cleaning composition and process for removal of organic, organometallic and metal oxide residues from substrates. More particularly, it relates to such a composition and process for removing semiconductor device fabrication residues from semiconductor device substrates, such as etching residues after plasma etching processes in the fabrication of integrated circuits on silicon wafers and similar processes. Most especially, it relates to such a composition and process which is effective for the removal of these materials while avoiding substantial attack on metal or insulation layers employed in integrated circuits, including titanium layers.

[0004] 2. Description of the Prior Art

[0005] As integrated circuit manufacturing has become more complex and the dimensions of circuit elements fabricated on silicon or other semiconductor wafers have become smaller, continued improvement in techniques used to remove residues formed from such materials has been required. Oxygen plasma oxidation is often used for removal of photoresist or other polymeric materials after their use during the fabrication process has been completed. Such high energy processes typically result in the formation of organometallic and other residues on sidewalls of the structures being formed in the fabrication process.

[0006] A variety of metal and other layers are commonly employed in integrated circuit fabrication, including aluminum, aluminum/silicon/copper, titanium, titanium nitride, titanium/tungsten, tungsten, silicon oxide, polysilicon crystal, and the like. The use of such different layers results in the formation of different organometallic residues in the high energy processes. In addition to being effective for removing such residues, stripping and cleaning compositions should also not attack the different metallurgies or insulation layers used in integrated circuit fabrication.

[0007] A variety of residue removal compositions and processes suitable for integrated circuit fabrication have been developed and marketed by EKC Technology, Inc., the assignee of the present application. Some of these compositions and processes are also useful for stripping photoresist, polyimide or other polymeric layers from substrates in integrated circuit fabrication, and EKC has also developed a variety of compositions and processes for stripping such polymeric layers from substrates in integrated circuit fabrication. Such compositions and processes are disclosed in the following commonly assigned issued patents: U.S. Pat. No. 5,482,566, issued Jan. 9, 1996 to Lee; U.S. Pat. No. 5,399,464, issued Mar. 21, 1995 to Lee; U.S. Pat. No. 5,381,807, issued Jan. 17, 1995 to Lee; U.S. Pat. No. 5,334,332, issued Aug. 2, 1994 to Lee; U.S. Pat. No. 5,279,771, issued Jan. 18, 1994 to Lee; U.S. Pat. No. 4,824,763, issued Apr. 25, 1989 to Lee and U.S. Pat. No. 4,395,348, issued Jul. 26, 1983 to Lee. These compositions have achieved substantial success in integrated circuit fabrication applications. However, further development of integrated circuits and their fabrication processes have created a need for improvement in residue removal compositions and processes.

[0008] As a result of a continuous effort to decrease critical dimension size in the integrated circuit industry, such as in the fabrication of sub-micron size devices, etching residue removal and substrate compatibility with chemicals employed in wet processing is becoming more and more critical for obtaining acceptable yield in very large scale integration (VLSI) and ultra large scale integration (ULSI) processes. The composition of such etching residue is generally made up of the etched substrates, underlying substrate, photoresist and etching gases. The substrate compatibility of the wafers with wet chemicals is highly dependent on the processing of the polysilicon, multilevel interconnection dielectric layers and metallization in thin film deposition, etching and post-etch treatment of the wafers, which are often quite different from one fabrication process to another. Some of the above compositions have produced corrosion on certain metal substrates, such as those including a titanium metal layer. Titanium has become more widely used in semiconductor manufacturing processes. It is employed both as a barrier layer to prevent electromigration of certain atoms and as an antireflector layer on top of other metals.

SUMMARY OF THE INVENTION

[0009] Accordingly, it is an object of this invention to provide an improved composition for residue removal and process using such a composition suitable for meeting current semiconductor fabrication requirements.

[0010] It is another object of the invention to provide such a composition and process which is suitable for removing residues from wafers and other substrates including one or more titanium metal layers without substantial attack on such titanium layers.

[0011] The attainment of these and related objects may be achieved through use of the residue removal composition and process herein disclosed. A residue removal composition in accordance with this invention comprises a two carbon atom linkage alkanolamine compound, gallic acid or catechol, optionally, an aqueous hydroxylamine solution, and desirably a balance of water or another suitable polar solvent. A process for removing a residue from a substrate in accordance with this invention comprises contacting the substrate with a composition that contains a two carbon atom linkage alkanolamine compound for a time and at a temperature sufficient to remove the residue from the substrate.

[0012] In practice, we have found that use of a two carbon atom linkage alkanolamine compound gives a residue removing composition that attacks titanium substantially less than prior compositions. At the same time, the two carbon atom linkage alkanolamine compound containing composition gives equivalent performance as a residue removing composition.

[0013] The attainment of the foregoing and related objects, advantages and features of the invention should be more readily apparent to those skilled in the art, after review of the following more detailed description of the invention, taken together with the drawings, in which:

BRIEF DESCRIPTION OF THE DRAWINGS

[0014] FIGS. 1-8 are scanning electron microscope (SEM) photographs showing comparative results achieved using the composition and process of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0015] The two carbon atom linkage alkanolamine compounds suitable for use in the invention have the structural formula

[0016] wherein X and Y are, independently in each case, hydrogen, methyl or ethyl, and R is hydrogen or an alkyl group containing from 1 to 4 carbon atoms. The two carbon atom linkage alkanolamine compounds useful in the present invention preferably have relatively high boiling points, such as for example, 75° C. or above. Preferred specific examples of such two carbon atom linkage alkanolamine compounds include monoethanolamine and monoisopropanolamine.

[0017] The composition desirably contains at least about 10% by weight of at least one two carbon atom linkage alkanolamine compound, from about 5% to about 40% by weight of gallic acid, catechol or other chelating agent, and optionally, up to about 50 percent by weight of a 50% by weight aqueous hydroxylamine solution. The balance of the composition is desirably made up of water, preferably high purity deionized water, or another suitable polar solvent. The solvents can be used singly or as mixtures. The composition preferably includes from about 10% to about 80% by weight of at least one two carbon atom linkage alkanolamine compound, from about 5% to about 30% by weight of the gallic acid or catechol, from about 10% to about 30% of the hydroxylamine solution, with the remaining balance preferably being water or other suitable polar solvent.

[0018] In practice, it appears that the catechol or gallic acid enhances the ability of the two carbon atom linkage alkanolamine compound to remove the residue. At the same time, the presence of the catechol, gallic acid or other chelating agent helps to prevent attack on titanium metallurgy.

[0019] Suitable examples of polar solvents for the composition, in addition to water, include dimethyl sulfoxide, ethylene glycol, ethylene glycol alkyl ether, diethylene glycol alkyl ether, triethylene glycol alkyl ether, propylene glycol, propylene glycol alkyl ether, dimethyl sulfoxide, N-substituted pyrrolidone, ethylenediamine and ethylenetriamine. Additional polar solvents as known in the art can also be used in the composition of the present invention.

[0020] The residue cleaning compositions of the present composition are effective in removing organometallic and metal oxide residue from a variety of integrated circuit silicon wafer substrates, including metal layers, such as aluminum or titanium, oxide layers, such as silicon oxides, nitride layers, such as silicon nitride, and the like. The cleaning compositions of the present invention are also effective in removing organometallic and metal oxide residue generated on the substrate of etching equipment utilized in the fabrication of integrated circuits. Examples of commercially available etching equipment include that available from Lam Research, Tegal, Electrotech, Applied Materials, Tokyo Electron, Hitachi and the like.

[0021] The method of cleaning a substrate using the cleaning compositions of the present invention involves contacting a substrate having organometallic and metal oxide residue thereon with a stripping and cleaning composition of the present invention for a time and at a temperature sufficient to remove the residue. The substrate is generally immersed in the stripping and cleaning composition. The time and temperature are determined based on the particular material being removed from a substrate. Generally, the temperature is in the range of from about ambient or room temperature to about 120° C. and the contact time is from about 2 to 60 minutes.

[0022] The substrate may then be rinsed in a polar solvent, such as isopropyl alcohol, followed by a deionized water rinse. The substrate is then mechanically dried, such as with a spin drier, or nitrogen blow dried.

[0023] The following represent non-limiting examples and describe the invention further.

[0024] Examples of cleaning compositions according to the present invention suitable for removing resist or other organic residues from a substrate are set forth in Table I below. TABLE 1 Cleaning Alkanolamine Gallic Acid/Catechol Hydroxyl- Additional Composition Wt. % Wt. % Amine Wt. % Solvent Wt. % A 60% DGA  5% Catechol 30% (50 Wt % Aq. Sol'n) B 55% MIPA 10% gallic acid 30% (50 Wt 5% Water % Aq. Sol'n.) C 60% MEA 35% (50 Wt 5% Water % Aq. Sol'n.) D 60% MEA  5% gallic acid 35% (50 Wt % Aq. Sol'n.) E 60% MIPA  5% Catechol 35% (50 Wt % Aq. Sol'n.) F 30% MEA 10% Catechol 30% (50 Wt 5% Water 25% MIPA % Aq. Sol'n.) G 30% MEA 10% gallic acid 30% (50 Wt 5% Water 25% MIPA % Aq. Sol'n.) H 55% DGA 10% galhic acid 30% (50 Wt 5% Water % Aq. Sol'n.)

EXAMPLE 1

[0025] A semiconductor wafer having a patterned metal stack consisting of TiN/Al/Ti/TiN/SiO₂ was treated with composition A at 75° C. for 30 minutes to remove process reside from the wafer, for comparative purposes. FIG. 1 is a scanning electron microscope (S EM) photograph of the wafer after this treatment. Substantial undercutting of both Ti layers are visible in this photograph.

EXAMPLE 2

[0026] A semiconductor wafer having a patterned metal stack consisting of TiN/Al/Ti/TiN/Ti/SiO₂ was treated with composition B at 75° C. for 30 minutes to remove process reside from the wafer. FIG. 2 is a SEM photograph of the wafer after this treatment. No undercutting of the lower Ti layer is visible, and a slight undercutting of the upper Ti layer is visible.

EXAMPLE 3

[0027] A semiconductor wafer having a patterned metal stack consisting of TiN/Al/Ti/TiN/Ti/SiO₂ was treated with composition C at 75° C. for 30 minutes to remove process reside from the wafer, as a control. FIG. 3 is a SEM photograph of the wafer after this treatment Undercutting of both Ti layers is visible.

EXAMPLE 4

[0028] A semiconductor wafer having a patterned metal stack consisting of TiN/Al/Ti/TiN/Ti/SiO₂ was treated with composition D at 75° C. for 30 minutes to remove process reside from the wafer. FIG. 4 is a SEM photograph of the wafer after this treatment A slight undercutting of the lower Ti layer is visible, and no undercutting of the upper Ti layer is visible.

EXAMPLE 5

[0029] A semiconductor wafer having a patterned metal stack consisting of W/Ti/SiO₂ was treated with composition E at 75° C. for 30 minutes to remove process reside from the wafer. FIG. 5 is a SEM photograph of the wafer after this treatment. No undercutting of the Ti layer is visible.

EXAMPLE 6

[0030] A semiconductor wafer having a patterned metal stack consisting of TiN/Ti/Al/Ti/TiN/BPSG (boron phosphosilicate glass) was treated with composition F at 75° C. for 30 minutes to remove process reside from the wafer. FIG. 6 is a SEM photograph of the wafer after this treatment No undercutting of the Ti layers is visible.

EXAMPLE 7

[0031] A semiconductor wafer having a patterned metal stack consisting of TiN/Al/Ti/TiN/SiO₂ was treated with composition G at 75° C. for 30 minutes to remove process reside from the wafer. FIG. 7 is a SEM photograph of the wafer after this treatment No undercutting of the Ti layers is visible.

EXAMPLE 8

[0032] A semiconductor wafer having a patterned metal stack consisting of TiN/Al/Ti/TiN/Ti/SiO₂ was treated with composition H at 75° C. for 30 minutes to remove process reside from the wafer, for comparative purposes. FIG. 8 is SEM photograph of the wafer after this treatment Undercutting of the Ti layers is visible.

[0033] The above examples show that compositions B, D, E, F and G successfully remove residues from substrates having a titanium metallurgy while reducing or eliminating attack on the titanium metallurgy. Increased amounts of catechol or gallic acid produce an improved reduction of attack on the titanium metallurgy. The comparative compositions A, C and H all show substantial attack on the titanium metallurgy, even when a two carbon atom linkage alkanolamine compound is used in the absence of gallic acid or catechol. When gallic acid or catechol is used with an alkanolamine compound other than a two carbon atom linkage alkanolamine compound, the gallic acid or catechol does not show a similar reduction of attack of the composition on the titanium metallurgy.

[0034] It should now be readily apparent to those skilled in the art that a novel composition and process capable of achieving the stated objects of the invention has been provided. The improved two carbon atom linkage alkanolamine compound based composition and process using such a composition of this invention is suitable for meeting current semiconductor fabrication requirements. The composition and process is suitable for removing photoresist residues and other residues from wafers and other substrates including one or more titanium metal layers without substantial attack on such titanium layers.

[0035] It should further be apparent to those skilled in the art that various changes in form and details of the invention as shown and described may be made. It is intended that such changes be included within the spirit and scope of the claims appended hereto. 

What is claimed is:
 1. A composition for removal of process residue from a substrate, which comprises: (a) a a two carbon atom linkage alkanolamine compound, and (b) a chelating agent.
 2. The composition of claim 1 in which the two carbon atom linkage alkanolamine compound has the formula:

wherein X and Y are, independently in each case, hydrogen, methyl or ethyl, and R is hydrogen or an alkyl group containing from 1 to 4 carbon atoms.
 3. The composition of claim 1 additionally comprising: (c) water or a polar organic solvent.
 4. The composition of claim 3 in which the polar organic solvent comprises dimethyl sulfoxide, ethylene glycol, ethylene glycol alkyl ether, diethylene glycol alkyl ether, triethylene glycol alkyl ether, propylene glycol, propylene glycol alkyl ether, dimethyl sulfoxide, N-substituted pyrrolidone, ethylenediamine or ethylenetriamine.
 5. The composition of claim 1 additionally comprising: (c) an aqueous hydroxylamine solution.
 6. The composition of claim 1 in which the two carbon atom linkage alkanolamine compound is present in an amount of at least about 10 percent by weight.
 7. The composition of claim 6 in which the chelating agent is gallic acid or catechol.
 8. The composition of claim 7 in which the gallic acid or catechol is present in an amount of from about 5 percent to about 50 percent by weight.
 9. The composition of claim 8 additionally comprising: (c) up to about 50 percent by weight of an aqueous hydroxylamine solution.
 10. The composition of claim 6 in which the two carbon atom linkage alkanolamine compound is present in an amount of from about 10 percent by weight to about 80 percent by weight.
 11. The composition of claim 10 in which the chelating agent is gallic acid or catechol and is present in an amount of from about 5 percent to about 30 percent by weight.
 12. The composition of claim 11 additionally comprising: (c) from about 10 percent by weight to about 30 percent of an about 50 percent by weight aqueous hydroxylamine solution.
 13. A process for removal of process residue from a substrate, which comprises contacting the substrate with a composition comprising: (a) a a two carbon atom linkage alkanolamine compound, and (b) a chelating agent for a time and at a temperature sufficient to remove the process residue from the substrate.
 14. The process of claim 13 in which the two carbon atom linkage alkanolamine compound has the formula:

wherein X and Y are, independently in each case, hydrogen, methyl or ethyl, and R is hydrogen or an alkyl group containing from 1 to 4 carbon atoms.
 15. The process of claim 13 in which the composition additionally comprises: (c) water or a polar organic solvent.
 16. The process of claim 15 in which the polar organic solvent comprises dimethyl sulfoxide, ethylene glycol, ethylene glycol alkyl ether, diethylene glycol alkyl ether, triethylene glycol alkyl ether, propylene glycol, propylene glycol alkyl ether, dimethyl sulfoxide, N-substituted pyrrolidone, ethylenediamine or ethylenetriamine.
 17. The process of claim 13 in which the composition additionally comprises: (c) an aqueous hydroxylamine solution.
 18. The process of claim 14 in which the two carbon atom linkage alkanolamine compound is present in an amount of at least about 10 percent by weight.
 19. The process of claim 14 in which the chelating agent is gallic acid or catechol.
 20. The process of claim 19 in which the gallic acid or catechol is present in an amount of from about 5 percent to about 50 percent by weight.
 21. The process of claim 20 in which the composition additionally comprises: (c) up to about 50 percent by weight of an aqueous hydroxylamine solution.
 22. The process of claim 18 in which the two carbon atom linkage alkanolamine compound is present in an amount of from about 10 percent by weight to about 80 percent by weight.
 23. The composition of claim 22 in which the chelating agent is gallic acid or catechol and is present in an amount of from about 5 percent to about 30 percent by weight.
 24. The process of claim 23 in which the composition additionally comprises: (c) from about 10 percent by weight to about 30 percent of an about 50 percent by weight aqueous hydroxylamine solution.
 25. The process of claim 13 in which the temperature is in the range of from about room temperature to about 120° C.
 26. The process of claim 25 in which the contact time is from about 2 to 60 minutes. 